Maria Baskin

Water‐soluble chiral metallopeptoids

Metal ions play a significant role in the activity of biological systems including catalysis, recognition and folding. Therefore, introducing metal ions into peptidomimetic oligomers is a potential way for creating biomimetic metal complexes toward applications in sensing, recognition, drug design and catalysis. Herein we report the design, synthesis and characterization of water‐soluble chiral N‐substituted glycine oligomers, “peptoids,” with one and two distinct intramolecular binding sites for metal ions such as copper and cobalt. We demonstrate for the first time the incorporation of the chiral hydrophilic group (S)‐(+)‐1‐methoxy‐2‐propylamine (Nsmp) within peptoid sequences, which provides both chirality and water solubility. Two peptoids, a heptamer, and a dodecamer bearing two and four 8‐hydroxyquinoline (HQ) groups respectively as metal‐binding ligands, were synthesized on solid support using the submonomer approach. Using UV‐titrations and ESI‐MS analysis we demonstrate the creation of a novel metallopeptoid bearing two metal ions in distinct binding sites via intramolecular chelation. Exciton couplet circular dichroism (ECCD) demonstrated chiral induction from the chiral non‐helical peptoids to the metal centers.

A Pure Polyproline Type I-like Peptoid Helix via Metal Coordination

Peptoids, N-substituted glycine oligomers, are an important class of foldamers that can adopt polyproline-type helices (PP-I and PP-II), given that the majority of their sequence consists of chiral, bulky side chains. Herein a new approach for the stabilization of a pure PP-I-like peptoid helix through metal coordination is introduced. A systematic spectroscopic study was performed on a series of peptoid heptamers bearing two 8-hydroxyquinoline ligands at fixed positions, and a mixture of chiral benzyl and alkyl substituents in varied positions along the peptoid backbone. When the benzyl groups are located at the 3rd and 4th positions, the peptoid (7P6) gives upon Cu2+ binding a circular dichroism (CD) signal similar to that of a PP-I helix. Exciton couplet CD spectroscopy and EPR spectroscopy, as well as modifications to the length of 7P6 and derivatization through acetylation provided insights into the unique folding of 7P6 upon Cu binding, showing that it is led by two competing driving forces, namely coordination geometry and sequence.

Folding of Unstructured Peptoids and Formation of Hetero-Bimetallic Peptoid Complexes upon Side-Chain-to-Metal Coordination

Metal ions initiate peptoids helicity that lead to positive allosteric cooperativity.

Band offsets at amorphous-crystalline Al2O3–SrTiO3 oxide interfaces

2D electron gases (2DEGs) formed at oxide interfaces provide a rich testbed for fundamental physics and device applications. While the discussion of the physical origins of this phenomenon continues, the recent discovery of oxide 2DEGs at non-epitaxial interfaces between amorphous and crystalline oxides provides useful insight into this debate. Furthermore, using amorphous oxides offers a low-cost route towards realizing 2DEGs for device applications. In this work, the band offsets of a simple model system of an amorphous-crystalline oxide interface are investigated. The model system consists of amorphous Al2O3 grown on single-crystalline (001) SrTiO3. X-ray photoelectron spectroscopy is employed to study the chemical states, bandgap, and band offsets at the interface. The density of ionic defects near the interface is found to be below the detection limit, and the interface is found to be insulating. Analysis of the relative band structure yields significant interfacial barriers, exceeding 1.05 eV for holes and 2.0 eV for electrons. The barrier for holes is considerably larger than what is known for related material systems, outlining the promise of using amorphous Al2O3 as an effective and simple insulator, an important building block for oxide-based field effect devices.2D electron gases (2DEGs) formed at oxide interfaces provide a rich testbed for fundamental physics and device applications. While the discussion of the physical origins of this phenomenon continues, the recent discovery of oxide 2DEGs at non-epitaxial interfaces between amorphous and crystalline oxides provides useful insight into this debate. Furthermore, using amorphous oxides offers a low-cost route towards realizing 2DEGs for device applications. In this work, the band offsets of a simple model system of an amorphous-crystalline oxide interface are investigated. The model system consists of amorphous Al2O3 grown on single-crystalline (001) SrTiO3. X-ray photoelectron spectroscopy is employed to study the chemical states, bandgap, and band offsets at the interface. The density of ionic defects near the interface is found to be below the detection limit, and the interface is found to be insulating. Analysis of the relative band structure yields significant interfacial barriers, exceeding 1.05 eV for ho...